Robert Mulliken

NATIONAL ACADEMY OF SCIENCES ROBERT SANDERSON MULLIKEN 1896–1986 A Biographical Memoir by R. STEPHEN BERRY Biographical Memoirs, VOLUME 78 PUBLISHED 2000 BY THE NATIONAL ACADEMY PRESS WASHINGTON, D.C. Photo credit: Photo by Harris & Ewing, Washington, D.C. ROBERT SANDERSON MULLIKEN June 7, 1896-October 31, 1986 BY R. STEPHEN BERRY OBERT S. MULLIKEN WAS a quiet, soft-spoken man, yet so R single-minded and determined in his devotion to understanding molecules that he came to be called “Mr. Molecule.” If any single person’s ideas and teachings dominated the development of our understanding of molecular structure and spectra, it surely was Robert Mulliken. From the begin- ning of his career as an independent scientist in the mid- 1920s until he published his last scientific papers in the early 1980s, he guided an entire field through his penetrat- ing solutions of outstanding puzzles, his identification (or discovery) and analysis of the new major problems ripe for study, and his creation of a school—the Laboratory of Molecular Structure and Spectroscopy or LMSS at the University of Chicago, during its existence the most important center in the world for the study of molecules. Robert’s background led him naturally into academic science. He was born in Newburyport, Massachusetts, in a house built by his great-grandfather in about 1798. His father, Samuel Parsons Mulliken, was a professor of chemistry at MIT, which made him a daily commuter between Newburyport and Boston. Samuel Mulliken and his child- hood friend and later MIT colleague Arthur A. Noyes were 3 4 BIOGRAPHICAL MEMOIRS strong influences stirring Robert’s interests in science. As a high school student, Robert decided against philosophy as a career and opted for science. He attended MIT as an undergraduate, receiving his B.S. in chemistry in 1917. He then took on a wartime job studying poison gases in a laboratory at American University under the direction of a cer- tain Lieutenant James Bryant Conant, then of the Chemi- cal Warfare Service. Mulliken entered the Chemical Warfare Service himself, rising to private first class, but left the service when he contracted influenza in 1918. When he recov- ered, he worked for the New Jersey Zinc Company until he entered graduate school at the University of Chicago in the fall of 1919. As a graduate student in chemistry at Chicago, Robert worked under the direction of W. D. Harkins, first on surface tension and then on isotope separation, particularly of mercury isotopes. The method used in his thesis was “irre- versible evaporation” and distillation. Robert found that a dirty surface on the mercury aided the separation consider- ably; this concept, later called a boundary layer or diffusion membrane, played an integral role in the Manhattan Project. Robert conceived and tried centrifugation, but as he said fifty-five years later, the centrifuge then was simply too crude. He also considered photochemical separation, but never published anything on the subject. At Chicago, Robert became interested in the interpretation of valence and chemical bonding through the papers of Irving Langmuir and G. N. Lewis. He encountered the old quantum theory through two enthusiastic courses of lectures by Robert A. Millikan, but was uneasy about the theory; “a disorganized chaos” was the description Mulliken used for it in reminiscences written in 1965. Nevertheless, Robert succeeded in applying it in 1924-25 to the interpretation of a particular molecular spectrum, assigned initially ROBERT SANDERSON MULLIKEN 5 by Wilfred Jevons to the boron nitride molecule, BN. Mulliken showed that the spectrum was that of boron oxide despite the preparation involving no apparent oxygen-containing substances. Jevons was pressed by a zealous department head to publish a note insisting on the initial assignment. Then, at the urging of R. T. Birge, Mulliken wrote directly to Jevons, visited him in England in 1925, and the two men settled the matter amicably and remained friends thereafter. Robert held a National Research Council Fellowship at that time and was working at Harvard after completing his Ph.D. in 1922. He had wanted to study beta-ray spectroscopy with Ernest Rutherford at Manchester, but the fellowship board felt that his physics background was not strong enough and urged him to select a more chemical topic. Conse- quently he carried out many experiments in molecular spectroscopy largely under the guidance of E. C. Kemble and F. A. Saunders. At that time, a coterie of young, enthusiastic American scientists grew up in Cambridge, a group including Mulliken, Samuel Allison, F. A. Jenkins, J. R. Oppenheimer, John Van Vleck, Gregory Breit, Harold Urey, and John Slater. They were not all in Cambridge at the same time, but for the most part they knew one another, and there were several close friendships among them. Like most of that group, Mulliken made his early pil- grimage to Europe in the summer of 1925. This was just the threshold time of modern quantum mechanics. Robert, like several of his contemporaries, had been trying to give orga- nization to the states and spectra of diatomic molecules. This subject was, from his later reminiscences, a lively part of many of the discussions he had with colleagues and dis- tinguished senior scientists in London, Oxford, Cambridge, Copenhagen, and perhaps most important, Göttingen. There he met Max Born, James Franck (who, of course, later joined the faculty of the University of Chicago), Otto Oldenberg, 6 BIOGRAPHICAL MEMOIRS Hertha Sponer, V. Kondratiev, V. I. Semenov, A. Terenin, and especially Born’s assistant Fredrich Hund. The rela- tionship between them became one of the most fruitful in the twentieth century in the history of the interpretation of the structure of matter and the nature of chemical bonds. Even in 1925, a year before the first papers were published on quantum mechanics, Mulliken and Hund began to conceive an analogue for molecules of the “building-up principle” or “Aufbauprinzip” introduced by Niels Bohr to explain the structures of atoms and the Periodic Table. Their notion was that electrons in molecules would have quan- tized orbits like those introduced by Bohr and developed by Sommerfeld. These orbits would define successive shells like their atomic counterparts. However, the orbits in molecules would extend throughout the molecule, encircling two or more nuclei. After their meeting, Mulliken and Hund corresponded and both published on the subject in 1926 and 1927. But, as soon as they knew of the matrix mechanics of Heisenberg and the wave mechanics of Schrödinger, both realized that would be the correct direction for them. Mulliken probably learned first about Heisenberg’s work from a lecture in 1926 by Max Born. He felt quite inad- equately trained, especially in mathematics, for this new kind of physics—although it seems now like something he could have learned in a week or two. Schrödinger’s formu- lation, which was based on the second-order differential equations that everybody learned, “was somewhat of a relief that it wasn’t so bad.” Mulliken returned to Göttingen in 1927, after the hydro- gen atom had been worked out by Pauli with matrix mechanics and by Schrödinger with wave mechanics. That summer was the time Hund and Mulliken worked out their basic interpretation of the spectra of diatomic molecules and their generalization of atomic orbitals, the standing- ROBERT SANDERSON MULLIKEN 7 wave, stationary states of electrons in atoms, to “molecular orbitals,” the molecular counterparts. Robert’s strengths were a deep knowledge of molecular spectra and a capacity to invent phenomenological and empirical interpretations; Hund brought quantitative and mathematical insights, a greater mastery of the new theories, and a specific vector model for quantum systems. They shared a view of stationary states of electrons in molecules and of the analogy between atoms and molecules. By 1928 they had both written their first papers that went beyond the old quantum theory, and molecular orbitals were born. Remarkably, especially in light of their long friendship and profound mutual respect, the two men never published a joint paper. Also during the summer of 1927 in Zürich, Mulliken met Schrödinger, whose chair, Mulliken recalled later, collapsed spontaneously during their conversation. Schrödinger then introduced him to W. Heitler and F. London, who were just developing their electron pair theory of the chemical bond. This approach, close to Langmuir’s and Lewis’s, was to become a rival to the molecular orbital approach until John Slater, some years later, showed that both were approxima- tions and suitable starting points from which a common, accurate theoretical picture could be achieved. Upon see- ing it for the first time, Robert was not enthusiastic. How- ever, he was deeply involved in developing his own ideas and did not care to stop to learn, evaluate, and incorporate such different ideas from others. Linus Pauling and John Slater, however, quickly absorbed the ideas and the Heitler- London-Slater-Pauling valence bond theory became another item in the theorist’s bag of tools. There were difficulties inherent in valence bond theory that did not appear in the Hund-Mulliken molecular orbital theory, which Mulliken recognized. Mulliken objected particularly to how “Pauling made a special point in making everything sound as simple 8 BIOGRAPHICAL MEMOIRS as possible and in that way making it [valence bond theory] very popular with chemists but delaying their understanding of the true [complexity of molecular structure].” Mulliken’s respect for Hund and Slater endured throughout his life; he felt that his Nobel Prize should most properly have been shared with them. Between the two trips to Europe, Mulliken became an assistant professor in the Department of Physics at New York University.

Load more